Display options
Share it on

Angew Chem Int Ed Engl. 2017 Oct 23;56(44):13747-13751. doi: 10.1002/anie.201707914. Epub 2017 Oct 02.

Electron-Transfer and Hydride-Transfer Pathways in the Stoltz-Grubbs Reducing System (KOtBu/Et.

Angewandte Chemie (International ed. in English)

Andrew J Smith, Allan Young, Simon Rohrbach, Erin F O'Connor, Mark Allison, Hong-Shuang Wang, Darren L Poole, Tell Tuttle, John A Murphy

Affiliations

  1. Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL, UK.
  2. Flexible Discovery Unit, GlaxoSmithKline Medicines Research Centre, Gunnels Wood Road, Stevenage, SG1 2NY, UK.

PMID: 28892585 PMCID: PMC5656899 DOI: 10.1002/anie.201707914

Abstract

Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and S

© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Keywords: density-functional calculations; electron transfer; hydrides; reaction mechanisms; silicon

References

  1. J Am Chem Soc. 2014 Dec 24;136(51):17818-26 - PubMed
  2. Angew Chem Int Ed Engl. 2016 Mar 24;55(14):4492-6 - PubMed
  3. J Am Chem Soc. 2015 Jul 8;137(26):8617-22 - PubMed
  4. J Am Chem Soc. 2013 Jul 31;135(30):10934-7 - PubMed
  5. Angew Chem Int Ed Engl. 2014 Jan 7;53(2):474-8 - PubMed
  6. Angew Chem Int Ed Engl. 2012 Apr 10;51(15):3673-6 - PubMed
  7. J Comput Chem. 2003 Apr 30;24(6):669-81 - PubMed
  8. J Am Chem Soc. 2007 Nov 7;129(44):13368-9 - PubMed
  9. J Am Chem Soc. 2017 May 24;139(20):6880-6887 - PubMed
  10. Angew Chem Int Ed Engl. 2013 Feb 18;52(8):2239-42 - PubMed
  11. J Chem Phys. 2006 Nov 21;125(19):194310 - PubMed
  12. J Am Chem Soc. 2017 May 24;139(20):6867-6879 - PubMed
  13. Nature. 2015 Feb 5;518(7537):80-4 - PubMed
  14. J Org Chem. 2014 Mar 21;79(6):2522-37 - PubMed
  15. Angew Chem Int Ed Engl. 2007;46(27):5178-83 - PubMed
  16. Angew Chem Int Ed Engl. 2005 Feb 18;44(9):1356-60 - PubMed
  17. J Am Chem Soc. 2016 Jun 15;138(23):7402-10 - PubMed
  18. Nat Protoc. 2015 Dec;10(12):1897-903 - PubMed
  19. Angew Chem Int Ed Engl. 2017 Oct 23;56(44):13747-13751 - PubMed
  20. Angew Chem Int Ed Engl. 2015 Sep 14;54(38):11236-9 - PubMed
  21. Beilstein J Org Chem. 2017 Feb 13;13:267-284 - PubMed

Publication Types